Apparatus for Forming Thin Film

ABSTRACT

A shower head having a plurality of ejection holes for supplying an organic metal gas at uniform density to the surface of a substrate and a plurality of ejection holes for supplying an oxidizing gas at uniform density to the same is provided in a reaction furnace of an MOCVD system. A heater for heating the inside to a temperature higher than the thermal decomposition point of the organic metal gas but lower than the film forming temperature is provided in the vicinity of the substrate-side surface of the shower head.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation of application Ser. No. 10/311,880 filed Mar. 12, 2003, which is a 371 national stage entry of international patent application no. PCT/JP01/05406, filed Jun. 25, 2001, designating the United States of America, and published in Japan on Dec. 27, 2001, as WO 2001/99165, the entire disclosures of which are incorporated herein by reference. Priority is claimed based on Japanese patent application no. 2000-188821, filed Jun. 23, 2000.

1. TECHNICAL FIELD

The present invention relates to a thin film forming method and thin film forming apparatus for forming a thin film containing a metal element on a substrate by chemical vapor deposition which utilizes the thermal decomposition reaction of an organometallic compound.

2. BACKGROUND ART

An MOCVD (Metal Organic Chemical Vapor Deposition) has been conventionally known which forms a compound semiconductor film by utilizing the thermal decomposition reaction of an organometallic compound. This MOCVD can form a thin film made of a ferroelectric such as PZT, which is used in a semiconductor device such as a memory.

3. DISCLOSURE OF INVENTION Problem to be Solved by the Invention

To form a thin film made of a ferroelectric such as PZT on a semiconductor device, a film must be formed at a low temperature of 450° C. or less, and a sufficient film formation rate must be obtained. When a PZT film is to be formed, the uniformity in its composition must be ensured. In the conventional MOCVD, however, it is difficult to satisfy both the uniformity in composition of a thin film and a sufficient film forming rate.

In contrast, a technique for increasing the uniformities in composition and thickness of a thin film by using a shower head has been known. On the other hand, a technique for increasing a film formation rate by preheating an organic metal gas serving as a source gas and supplying it on a substrate has been known. There is thus provided a technique for preheating a source gas by a heater arranged between the shower head and a substrate in order to increase a film formation rate while using a shower head.

However, this technique has the following problem.

-   -   (a) In metal oxide film formation, an oxidizing gas is also         supplied to the substrate as the source gas. In this case, when         a heater is exposed, it is unpreferably oxidized.     -   (b) When preheating is performed near the gas introduction         portion of the shower head, a highly reactive component is         generated by preheating. Since this component easily attaches to         the inner wall of the shower head, the nozzles of the shower         head clog. In addition, when a multicomponent metal oxide film         such as a PZT film is to be formed, since some components         contained in the film are to be easily deposited by preheating         and others are not, the supply amount of only a certain         component may be reduced.

For these reasons, when preheating is performed before film formation, the uniformities in thickness and composition of a film in film formation degrade.

The present invention has been made to solve the above problem, and has as its object to provide a thin film forming method and thin film forming apparatus which can ensure the satisfactory composition of a thin film and the uniformity in thickness thereof, and increase a film formation rate.

Means of Solution to the Problem

In a thin film forming method of the present invention, an inside in the vicinity of a substrate-side surface of gas supply means for supplying an organic metal gas to a surface of a substrate at uniform density is heated to a temperature higher than a thermal decomposition point of an organic metal gas but lower than a film forming temperature.

As described above, the organic metal gas can be supplied to the surface of the substrate at uniform density by using the gas supply means. Heating a local portion immediately before the position of uniform supply of the organic metal gas from the gas supply means enables the thermal decomposition of the organic metal gas. In forming a thin film, e.g., a PZT film in which the uniformity in composition is very important, an intermediate product thermally decomposed without impairing the uniformity in composition can be supplied to the surface of the substrate. Therefore, a film formation rate can increase without impairing the uniformities in thickness and composition of the film.

In another thin film forming method of the present invention, an inside at only a periphery of an ejection hole for an organic metal gas, out of two gas ejection holes provided to gas supply means for supplying an organic metal gas and oxidizing gas to a surface of a substrate at uniform density, is heated to a temperature higher than a thermal decomposition point of an organic metal gas but lower than a film forming temperature.

As described above, since only the inside at the periphery of the ejection holes for the organic metal gas is heated to a temperature higher than the thermal decomposition point of the organic metal gas but lower than the film forming temperature, the organic metal gas can be thermally decomposed, thereby supplying a thermally decomposed intermediate product to the surface of the substrate.

In a thin film forming apparatus of the present invention, gas supply means having a plurality of ejection holes which supply an organic metal gas to a surface of the substrate at uniform density is provided in a reaction chamber, and a heater for heating the organic metal gas to a temperature higher than a thermal decomposition point of an organic metal gas but lower than a film forming temperature is incorporated near a substrate-side surface of the gas supply means.

As described above, the organic metal gas can be supplied to the surface of the substrate at uniform density by using the gas supply means. Heating, by a heater, a local portion immediately before the position of uniform supply of the organic metal gas from the gas supply means enables the thermal decomposition of the organic metal gas. In forming a thin film, e.g., a PZT film in which the uniformity in composition is very important, an intermediate product thermally decomposed without impairing the uniformity in composition can be supplied to the surface of the substrate. Therefore, a film formation rate can increase without impairing the uniformities in thickness and composition of the film.

In another thin film forming apparatus of the present invention, gas supply means having a plurality of first ejection holes which supply an organic metal gas to a surface of the substrate at uniform density and a plurality of second ejection holes which supply an oxidizing gas at uniform density are provided in a reaction chamber, and a heater for heating the organic metal gas to a temperature higher than a thermal decomposition point of an organic metal gas but lower than a film forming temperature is incorporated around the first ejection holes of the gas supply means.

As described above, since the periphery of the first ejection holes is heated by a heater to a temperature higher than the thermal decomposition point of the organic metal gas but lower than the film forming temperature, the organic metal gas can be thermally decomposed, thereby supplying the thermally decomposed intermediate product to the surface of the substrate.

4. BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a block diagram showing the arrangement of an MOCVD system according to an embodiment of the present invention;

FIG. 2 is a bottom view of a shower head shown in FIG. 1;

FIG. 3 is a sectional view of the shower head shown in FIG. 1; and

FIG. 4 is a plan view showing the pattern of a heater.

5. BEST MODE OF CARRYING OUT THE INVENTION

An embodiment of the present invention will be described in detail with reference to the accompanying drawings. FIG. 1 is a block diagram showing the arrangement of an MOCVD system according to an embodiment of the present invention.

In FIG. 1, reference numeral 1 denotes a source tank which holds a lead dibivaloylmethane complex Pb(DPM)₂; 2, a source tank which holds an organometallic compound source containing Ti, e.g., Ti(OiPr)₄; 3, a source tank which holds an organometallic compound source containing Zr, e.g., Zr(OtBt)₄; 4 to 7, mass-flow controllers for respectively controlling the flow rates of Pb(DPM)₂ gas, Ti(OiPr)₄ gas, Zr(OtBt)₄ gas, and NO₂ gas; 8, a reaction chamber; 9, a shower head serving as a gas supply means; and 10, a semiconductor substrate.

In this embodiment, the shower head 9 is used as a means for supplying an organic metal gas and oxidizing gas to the substrate 10 at uniform density. FIG. 2 is a bottom view of the shower head 9, and FIG. 3 is a sectional view of the shower head 9.

The lower structure of the shower head 9 is constructed by AlN ceramic plates 11 and 12 with good thermal conductivity. The ceramic plates 11 and 12 have a plurality of first ejection holes 13 for ejecting an organic metal gas and a plurality of second ejection holes 14 for ejecting an oxidizing gas (NO₂ gas). A heater 15 having a shape shown in FIG. 4 is printed on the upper surface of the AlN ceramic plate 11, which is formed to detour the ejection holes 13 and 14. The ceramic plates 11 and 12 accordingly sandwich the heater 15 therebetween. The heater 15 generates heat by making a current flow therein, so that the ceramic plates 11 and 12 are heated to a temperature (e.g., 240° C. when a PZT film is to be formed as in this embodiment) higher than the thermal decomposition point of the organic metal gas but lower than the film forming temperature.

In contrast, an upper structure 16 of the shower head 9 is made of Al. The upper structure 16 is heated by a heater (not shown) to a temperature (e.g., 200° C. when the PZT film is to be formed) higher than a temperature at which the organic metal gas can keep the vapor state but lower than the thermal decomposition point of the organic metal gas. When a buffer plate (not shown) made of Al₂O₃ or the like which has thermal conductivity lower than that of AlN is then formed between the AlN ceramic plate 12 and upper structure 16, the AlN ceramic plates 11 and 12 can be kept at a temperature higher than that of the upper structure 16.

A thin film forming method using the above-described MOCVD system will be described next. First, the source tank 1 is heated to evaporate the lead dibivaloylmethane complex Pb(DPM)₂, and the source tank 2 is simultaneously heated to evaporate an organometallic compound source Ti(OiPr)₄. The resultant Pb(DPM)₂ gas and Ti(OiPr)₄ gas and NO₂ gas are introduced into the evacuated reaction chamber 8. At this time, the pressure of the reaction chamber 8 is 0.005 torr, the flow rate of Pb(DPM)₂ gas is 0.2 sccm, the flow rate of Ti(OiPr)₄ gas is 0.14 sccm, the flow rate of NO₂ gas is 2.3 sccm, and a film forming temperature (substrate temperature) is 445° C. Under these conditions, Pb(DPM)₂ gas and Ti(OiPr)₄ gas pass through a path shown in FIG. 3 and are ejected from the ejection holds 13, and NO₂ gas passes through a path shown in FIG. 3 and is ejected from the ejection holes 14. With this processing, a crystal nucleus with a perovskite structure made of PbTiO₃ is formed on the substrate 10.

Successively, the source tank 3 is heated to evaporate Zr(OtBt)₄, and the resultant Zr(OtBt)₄ gas is introduced into the reaction chamber 8 together with the gases described above. The flow rate of Zr(OtBt)₄ gas is 0.175 sccm, and other conditions are the same as in the above description. Zr(OtBt)₄ gas is ejected from the ejection holes 13 together with Pb(DPM)₂ gas and Ti(OiPr)₄ gas. With this processing, a PZT film (PbZr_(x)Ti_(1-x)O₃ film) with the perovskite structure is formed on the substrate 10.

In this embodiment, the organic metal gas and oxidizing gas can be supplied to the surface of the substrate 10 at uniform density by using the shower head 9. The gas pipes to the shower head 9 are kept at a temperature (160 to 200° C. when the PZT film is to be formed) lower than thermally decomposition point of the organic metal gas, and the vicinity of the ejection holes 13 of the shower head 9 is heated to a temperature higher than the thermal decomposition point of the organic metal gas. With this processing, the organic metal gas which is easily thermally decomposed can be transported to the vicinity of the ejection holes of the shower head 9 and then thermally decomposed at the vicinities of the ejection holes 13. Therefore, the film formation rate can be made twice or more the conventional rate, from 10 nm/min to 25 nm/min. Note that the heater 15 heats both the ejection holes 13 and 14 in this embodiment. However, if the heater 15 heats only the vicinity of the ejection holes 13, the same effect can also be obtained.

Since the AlN has good thermal conductivity, variations in temperature of the substrate-side surface of the shower head 9 can be suppressed within ±1° C., thereby obtaining the satisfactory uniformity in temperature. Thus, the satisfactory composition and uniformity in thickness of the thin film formed on the substrate 10 can be ensured, and the film formation rate can be greatly increased as compared with that in the prior art.

Note that a nucleus forming process and a film forming process are performed at a high vacuum of 0.005 torr in this embodiment, but the film forming process may be performed at a low vacuum. That is, the lead dibivaloylmethane complex Pb(DPM)₂ and organometallic compound source Ti(OiPr)₄ are dissolved in an organic solvent (butyl acetate solution) and evaporated together with the organic solvent, and the resultant gas is introduced into the reaction chamber 8 at a pressure of 0.005 torr to form a nucleus. Successively, the organometallic compound source Zr(OtBt)₄ is dissolved in the organic solvent together with the above-described Pb(DPM)₂ and Ti(OiPr)₄ and evaporated with the organic solvent, and the resultant gas is introduced into the reaction chamber 8 at a pressure of about 0.1 to 0.5 torr to form a film. At this time, to make the respective partial pressures equal, an inert gas is introduced so as to make a total flow rate of gases about 20 to 100 times. This can increase the internal pressure of the shower head 9, thereby uniformity supplying the organic metal gas to the surface of the substrate.

This embodiment uses the post-mix type shower head 9 which supplies the organic metal gas and the oxidizing gas independently. However, a pre-mix type shower head for supplying the organic metal gas and oxidizing gas together may be used. In addition, the PZT film is formed on the substrate 10 in this embodiment, but the film is not obviously limited to the PZT film.

As described above, according to this embodiment, the inside of the vicinity of the substrate-side surface of the shower head 9 is heated to a temperature higher than the thermal decomposition point of the organic metal gas but lower than the film forming temperature. With this processing, the satisfactory composition and uniformity in thickness of the thin film formed on the substrate 10 can be ensured, and the film formation rate can be greatly increased as compared with that in the prior art. As a result, a thin film forming apparatus with good mass production can be realized. In addition, since the inside of the vicinity of the substrate-side surface of the shower head 9 is to be heated, the heater 15 is not exposed, thereby preventing the heater 15 from oxidation.

6. INDUSTRIAL APPLICABILITY

As has been described above, the present invention is suitable to forming a high-quality thin film. 

1. A thin film forming apparatus for forming a thin film containing a metal element on a substrate by chemical vapor deposition which utilizes a thermal decomposition reaction of an organometallic compound, said apparatus comprising: means for supplying an organic metal gas to a surface of the substrate at uniform density, the means for supplying gas provided in a reaction chamber and having a plurality of gas ejection holes, and means for heating the organic metal gas to a temperature higher than a thermal decomposition point of the organic metal gas but lower than a film forming temperature of the organic metal gas, the means for heating being incorporated at a substrate side of said means for supplying gas.
 2. A thin film forming apparatus for forming a thin film containing a metal element on a substrate by chemical vapor deposition which utilizes a thermal decomposition reaction of an organometallic compound, said apparatus comprising: means for supplying gases to a surface of the substrate at uniform density, the means for supplying gas provided in a reaction chamber and having a plurality of first gas ejection holes for supplying an organic metal gas to the surface of the substrate, and a plurality of second gas ejection holes for supplying an oxidizing gas to the surface of the substrate, and means for heating the organic metal gas to a temperature higher than a thermal decomposition point of the organic metal gas but lower than a film forming temperature of the organic metal gas, the means for heating being incorporated around the first gas ejection holes of said means for supplying gas.
 3. A thin film forming apparatus for forming a thin film containing a metal element on a substrate by chemical vapor deposition which utilizes a thermal decomposition reaction of an organometallic compound, said apparatus including means for supplying gas to a surface of the substrate, said means for supplying gas comprising: a lower portion including a plurality of gas ejection holes opposing the surface of the substrate and a first heating mechanism which heats the plurality of gas ejection holes to a first temperature, and an upper portion including a gas channel which supplies a gas to the plurality of gas ejection holes, and a second heating mechanism which heats the gas channel to a second temperature which is less than the first temperature.
 4. A thin film forming apparatus according to claim 3, wherein said means for supplying gas further comprises a buffer portion sandwiched between said lower portion and said upper portion, and a heat conductivity of said lower portion is less than a heat conductivity of said upper portion, but greater than a heat conductivity of said buffer portion.
 5. A thin film forming apparatus according to claim 4, wherein said upper portion is made of aluminum, said buffer portion comprises an Al₂O₃ plate, and said second heating mechanism comprises a heater.
 6. A thin film forming apparatus according to claim 3, wherein the plurality of gas ejection holes include: a plurality of first gas ejection holes for ejecting an organic metal gas, and a plurality of second gas ejection holes for ejecting an oxidizing gas.
 7. A thin film forming apparatus according to claim 6, wherein said lower portion comprises: a first plate having the plurality of first and second gas ejection holes, and a second plate having a first gas channel and a second gas channel, wherein the plurality of first gas ejection holes are in fluid communication with each other via the first gas channel, the plurality of second gas ejection holes are in fluid communication with each other via the second gas channel, and said first heating mechanism is disposed between said first plate and said second plate.
 8. A thin film forming apparatus according to claim 7, wherein said first plate and said second plate are made of an AlN ceramic material, and said first heating mechanism comprises a heater printed on said first plate. 